US5429760A - Refrigerant composition containing trifluoromethane and 1,1,1,2-tetrafluoroethane - Google Patents

Refrigerant composition containing trifluoromethane and 1,1,1,2-tetrafluoroethane Download PDF

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US5429760A
US5429760A US08/089,829 US8982993A US5429760A US 5429760 A US5429760 A US 5429760A US 8982993 A US8982993 A US 8982993A US 5429760 A US5429760 A US 5429760A
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refrigerant
weight
tetrafluoroethane
trifluoromethane
compressor
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US08/089,829
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Reinhold Doering
Hans Buchwald
Christoph von Eynatten
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Solvay Fluor GmbH
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Solvay Fluor und Derivate GmbH
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Assigned to SOLVAY FLUOR UND DERIVATE GMBH reassignment SOLVAY FLUOR UND DERIVATE GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DORING, REINHOLD, BUCHWALD, HANS, VON EYNATTEN, CHRISTOPH
Assigned to SOLVAY FLUOR UND DERIVATE GMBH reassignment SOLVAY FLUOR UND DERIVATE GMBH CORRECTIVE ASSIGNMENT Assignors: DOERING, REINHOLD, BUCHWALD, HANS, VON EYNATTEN, CHRISTOPH
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/04Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22All components of a mixture being fluoro compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/40Replacement mixtures
    • C09K2205/43Type R22
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25DREFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D2400/00General features of, or devices for refrigerators, cold rooms, ice-boxes, or for cooling or freezing apparatus not covered by any other subclass
    • F25D2400/30Quick freezing

Definitions

  • the present invention relates to novel compositions containing trifluoromethane and 1,1,1,2-tetrafluoroethane which are useful as refrigerants in refrigerating machines and air-conditioning systems.
  • the object of the invention is therefore to provide a suitable refrigerant for such refrigerating machines and air-conditioning systems.
  • a refrigerant composition consisting of from 2 to 8% by weight trifluoromethane and from 92 to 98% by weight 1,1,1,2-tetrafluoroethane.
  • FIG. 1 is a diagram of a compressor test stand (CO: compressor, LF: water-cooled liquefier, RE: restrictor, EV: expansion valve, MI: mixing tube, VO: volume- flow meter, A, B: branching points, I: inlet valve).
  • CO compressor
  • LF water-cooled liquefier
  • RE restrictor
  • EV expansion valve
  • MI mixing tube
  • VO volume- flow meter
  • A, B branching points
  • I inlet valve
  • Particularly preferred in this context are compositions containing R23 in an amount from 4 to 6% by weight.
  • compositions according to the invention are advantageously suitable, in particular, as refrigerants for the medium and low temperature range with evaporation temperatures (t 0 ) below -25° C., for example as refrigerants for the temperature range with t 0 between -25° C. to -45° C. in refrigerating machines such as, for example, upright freezers, chest freezers, cold chambers for aeronautical and scientific purposes or cold chambers for the rapid freezing of food, refrigeration plants for food markets, industrial large-scale refrigeration plants and air-conditioning appliances.
  • refrigerants for the medium and low temperature range with evaporation temperatures (t 0 ) below -25° C. for example as refrigerants for the temperature range with t 0 between -25° C. to -45° C.
  • refrigerating machines such as, for example, upright freezers, chest freezers, cold chambers for aeronautical and scientific purposes or cold chambers for the rapid freezing of food, refrigeration plants for food markets, industrial large-scale refrigeration plants and air-conditioning appliances
  • a pressure vessel was evacuated using a vacuum pump and then cooled down in a commercially available chest freezer to approximately -25° C. With the aid of a balance, the calculated amount of the higher-boiling component R134a was first metered into the pressure vessel, followed by the lower-boiling component R23.
  • a composition was produced which consisted of 95% by weight of R134a and 5% by weight of R23.
  • the compressor test stand works according to the partial-condensation method and comprises a circulation system which contains a compressor CO, a liquefier LF, a restrictor RE, an inlet valve I, an expansion valve EV, a mixing tube MI and a volume-flow meter VO, connected to one another via conduits.
  • the important stations of the compressor test stand used are shown diagrammatically in FIG. 1.
  • the pressure vessel containing the refrigerant was connected to the inlet valve, upstream of the expansion valve, of the evacuated compressor test stand. In order to transfer the refrigerant in liquid form into the evacuated refrigeration system, the pressure vessel was reheated to room temperature. The measurements were then carried out at the compressor test stand to determine the refrigeration characteristics according to the partial-condensation method. The measurements were carried out according to the standard specifications DIN 8977 and ISO 917.
  • the method is based on partitioning the refrigerant gas stream leaving the compressor CO at the branching point A into a refrigerant stream to be liquefied and a refrigerant stream to be throttled, which are recombined in point B after the mixture coming from the liquefier LF has been re-expanded via the expansion valve EV.
  • a mixing tube MI evaporation of the liquefied refrigerant proportion and mixing with the gas stream coming from the restrictor RE takes place.
  • the data measured are the temperatures and pressures at the inlet into the compressor (t 1h , p 0 ) and at the outlet from the compressor (t 2h , p c ), the effective volume flow V eff and the rotational speed of the compressor shaft.
  • composition according to the invention which contains R23 and R134a and which forms a non-azeotropic mixture, was additionally subjected in a known manner to p-v-T-x measurements according to the isochor principle. Taking into account the volumetric behavior data, obtained from the p-v-T-x measurements, of the composition according to the invention, and the test results on the compressor test stand, it was possible to determine or calculate, in a known manner via the compilation of the Mollier diagram, the following refrigeration characteristics for the refrigerant composition according to the invention:
  • the data determined on the basis of experimental measurements documents the useful refrigeration characteristics of the compositions according to the invention comprising R23 and R134a.
  • a high refrigerating capacity and a high performance coefficient are achieved at an acceptable pressure ratio.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)
  • Fats And Perfumes (AREA)

Abstract

Compositions containing trifluoromethane and 1,1,1,2-tetrafluoroethane which are useful as refrigerants in refrigerating machines and air-conditioning systems.

Description

BACKGROUND OF THE INVENTION
The present invention relates to novel compositions containing trifluoromethane and 1,1,1,2-tetrafluoroethane which are useful as refrigerants in refrigerating machines and air-conditioning systems.
In air-conditioning systems and refrigerating machines for the medium and low temperature range, the refrigerant chlorodifluoromethane (=R22) has hitherto been used in many cases. For ecological reasons, the use of the refrigerant R22 is now no longer desirable.
SUMMARY OF THE INVENTION
The object of the invention is therefore to provide a suitable refrigerant for such refrigerating machines and air-conditioning systems.
This and other objects of the invention are achieved by providing a refrigerant composition consisting of from 2 to 8% by weight trifluoromethane and from 92 to 98% by weight 1,1,1,2-tetrafluoroethane.
BRIEF DESCRIPTION OF THE DRAWING
The invention will be described in further detail hereinafter with reference to the accompanying drawing in which:
FIG. 1 is a diagram of a compressor test stand (CO: compressor, LF: water-cooled liquefier, RE: restrictor, EV: expansion valve, MI: mixing tube, VO: volume- flow meter, A, B: branching points, I: inlet valve).
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Compositions containing trifluoromethane (=R23) and 1,1,1,2-tetrafluoroethane (=R134a) have now been found which are suitable as refrigerants for refrigerating machines and air-conditioning systems.
The invention therefore relates to compositions which are suitable as refrigerants in refrigerating machines and air-conditioning systems and which comprise from 2 to 8% by weight of trifluoromethane (=R23) and from 92 to 98% by weight of 1,1,1,2-tetrafluoroethane (=R134a) and to their use as refrigerants in refrigerating machines and air-conditioning systems. Particularly preferred in this context are compositions containing R23 in an amount from 4 to 6% by weight.
The compositions according to the invention are advantageously suitable, in particular, as refrigerants for the medium and low temperature range with evaporation temperatures (t0) below -25° C., for example as refrigerants for the temperature range with t0 between -25° C. to -45° C. in refrigerating machines such as, for example, upright freezers, chest freezers, cold chambers for aeronautical and scientific purposes or cold chambers for the rapid freezing of food, refrigeration plants for food markets, industrial large-scale refrigeration plants and air-conditioning appliances.
The following examples are intended to illustrate the invention in further detail without limiting its scope.
EXAMPLES Example 1
Preparation of a Refrigerant Composition From R23 and R134a
A pressure vessel was evacuated using a vacuum pump and then cooled down in a commercially available chest freezer to approximately -25° C. With the aid of a balance, the calculated amount of the higher-boiling component R134a was first metered into the pressure vessel, followed by the lower-boiling component R23. A composition was produced which consisted of 95% by weight of R134a and 5% by weight of R23.
Example 2
Refrigeration Characteristics of a Refrigerant Composition Comprising R23 and R134a
Using the refrigerant composition prepared according to Example 1, comprising 5% by weight of R23 and 95% by weight of R134a, tests were carried out on a known type of compressor test stand (manufactured by Copeland) to determine the refrigeration characteristics. The compressor test stand works according to the partial-condensation method and comprises a circulation system which contains a compressor CO, a liquefier LF, a restrictor RE, an inlet valve I, an expansion valve EV, a mixing tube MI and a volume-flow meter VO, connected to one another via conduits. The important stations of the compressor test stand used are shown diagrammatically in FIG. 1.
The pressure vessel containing the refrigerant was connected to the inlet valve, upstream of the expansion valve, of the evacuated compressor test stand. In order to transfer the refrigerant in liquid form into the evacuated refrigeration system, the pressure vessel was reheated to room temperature. The measurements were then carried out at the compressor test stand to determine the refrigeration characteristics according to the partial-condensation method. The measurements were carried out according to the standard specifications DIN 8977 and ISO 917. The method is based on partitioning the refrigerant gas stream leaving the compressor CO at the branching point A into a refrigerant stream to be liquefied and a refrigerant stream to be throttled, which are recombined in point B after the mixture coming from the liquefier LF has been re-expanded via the expansion valve EV. In a mixing tube MI, evaporation of the liquefied refrigerant proportion and mixing with the gas stream coming from the restrictor RE takes place. The data measured are the temperatures and pressures at the inlet into the compressor (t1h, p0) and at the outlet from the compressor (t2h, pc), the effective volume flow Veff and the rotational speed of the compressor shaft.
The composition according to the invention, which contains R23 and R134a and which forms a non-azeotropic mixture, was additionally subjected in a known manner to p-v-T-x measurements according to the isochor principle. Taking into account the volumetric behavior data, obtained from the p-v-T-x measurements, of the composition according to the invention, and the test results on the compressor test stand, it was possible to determine or calculate, in a known manner via the compilation of the Mollier diagram, the following refrigeration characteristics for the refrigerant composition according to the invention:
______________________________________                                    
Evaporation temperature (t.sub.o)                                         
                            -39.8 to -27° C.                       
Pressure at the compressor inlet (p.sub.o)                                
                            1.05 bar                                      
Temperature at the compressor inlet                                       
                            1.82° C.                               
(t.sub.1h)                                                                
Pressure at the compressor outlet (p.sub.c)                               
                            10.60 bar                                     
Temperature at the compresser outlet                                      
                            97.73° C.                              
(t.sub.2h)                                                                
Liquefaction temperature (t.sub.c)                                        
                            38.5 to 25.6° C.                       
Effective refrigerant volume flow (V.sub.eff)                             
                            6.37 m.sup.3 /h                               
Performarice coefficient of the                                           
                     η.sub.RE                                         
                            2.10                                          
refrigeration process                                                     
Volumetric efficiency                                                     
                     λ                                             
                            0.698                                         
Isentropic compression efficiency                                         
                     η.sub.is                                         
                            0.716                                         
Refrigerating capacity                                                    
                     Q.sub.o                                              
                            1.37 kW                                       
Pressure ratio       p.sub.c /p.sub.o                                     
                            10.1                                          
Refrigerant mass flow                                                     
                     m.sub.R                                              
                            29.68 kg/h                                    
______________________________________                                    
The data determined on the basis of experimental measurements documents the useful refrigeration characteristics of the compositions according to the invention comprising R23 and R134a. Using the refrigerant compositions according to the invention, a high refrigerating capacity and a high performance coefficient are achieved at an acceptable pressure ratio.
The foregoing description and examples have been set forth merely to illustrate the invention and are not intended to be limiting. Since modifications of the disclosed embodiments incorporating the spirit and substance of the invention may occur to persons skilled in the art, the invention should be construed to include everything within the scope of the appended claims and equivalents thereof.

Claims (6)

What is claimed is:
1. A composition useful as a refrigerant in refrigerating machines and air-conditioning systems, consisting of from 2 to 8% by weight trifluoromethane and from 92 to 98% by weight 1,1,1,2-tetrafluoroethane.
2. A composition according to claim 1, which consists of from 4 to 6% by weight trifluoromethane and from 94 to 96% by weight 1,1,1,2-tetrafluoroethane.
3. In a method of refrigeration wherein a refrigerant is circulated between a heat absorbing station and a heat releasing station, the improvement comprising using as said refrigerant a composition consisting of from 2 to 8% by weight trifluoromethane and from 92 to 98% by weight 1,1,1,2-tetrafluoroethane.
4. A method according to claim 3, wherein said refrigerant composition consists of from 4 to 6% by weight trifluoromethane and from 94 to 96% by weight 1,1,1,2-tetrafluoroethane.
5. A method according to claim 3, wherein said heat absorbing station is maintained at a refrigerant evaporation temperature of below -25° C.
6. A method according to claim 5, wherein said heat absorbing station is maintained at a refrigerant evaporation temperature of between -25° C. and -45° C.
US08/089,829 1992-07-11 1993-07-12 Refrigerant composition containing trifluoromethane and 1,1,1,2-tetrafluoroethane Expired - Fee Related US5429760A (en)

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DE4222855A DE4222855A1 (en) 1992-07-11 1992-07-11 New refrigerant compositions
DE4222855.7 1992-07-11

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JP (1) JPH06166868A (en)
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AT (1) ATE133444T1 (en)
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CA (1) CA2100316A1 (en)
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DE (2) DE4222855A1 (en)
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HU (1) HUT67329A (en)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5705086A (en) * 1996-04-16 1998-01-06 Mobil Oil Corporation Refrigeration oils comprising esters of hindered alcohols
US6176102B1 (en) * 1998-12-30 2001-01-23 Praxair Technology, Inc. Method for providing refrigeration
US6327866B1 (en) 1998-12-30 2001-12-11 Praxair Technology, Inc. Food freezing method using a multicomponent refrigerant
WO2003027206A2 (en) * 2001-09-25 2003-04-03 American Standard International Inc. Replacement refrigerant for r410a
US20040061091A1 (en) * 2002-10-01 2004-04-01 Tieken James B. Refrigerant blend

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EP0430170A1 (en) * 1989-11-30 1991-06-05 Matsushita Electric Industrial Co., Ltd. Working fluid
EP0430130A1 (en) * 1989-11-29 1991-06-05 Matsushita Electric Industrial Co., Ltd. Working fluid
JPH03170591A (en) * 1989-11-30 1991-07-24 Matsushita Electric Ind Co Ltd Working fluid
JPH0496989A (en) * 1990-08-10 1992-03-30 Sanyo Electric Co Ltd Refritgerant composition and refrigerator
JPH0532961A (en) * 1991-07-25 1993-02-09 Daikin Ind Ltd Mixed cooling medium containing trifluoromethane
TW204364B (en) 1992-03-05 1993-04-21 Dairei Kk Carbon-fluoro coolant mixture

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US5304319A (en) * 1989-11-30 1994-04-19 Matsushita Electric Industrial Co., Ltd. Working fluid
JPH0655943B2 (en) * 1989-11-30 1994-07-27 松下電器産業株式会社 Working fluid
JP2580350B2 (en) * 1989-11-30 1997-02-12 松下電器産業株式会社 Working fluid
WO1993015163A1 (en) * 1992-02-03 1993-08-05 Allied-Signal Inc. Novel refrigerant compositions

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Publication number Priority date Publication date Assignee Title
EP0430130A1 (en) * 1989-11-29 1991-06-05 Matsushita Electric Industrial Co., Ltd. Working fluid
EP0430170A1 (en) * 1989-11-30 1991-06-05 Matsushita Electric Industrial Co., Ltd. Working fluid
JPH03170591A (en) * 1989-11-30 1991-07-24 Matsushita Electric Ind Co Ltd Working fluid
JPH0496989A (en) * 1990-08-10 1992-03-30 Sanyo Electric Co Ltd Refritgerant composition and refrigerator
JPH0532961A (en) * 1991-07-25 1993-02-09 Daikin Ind Ltd Mixed cooling medium containing trifluoromethane
TW204364B (en) 1992-03-05 1993-04-21 Dairei Kk Carbon-fluoro coolant mixture

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Title
DATABASE WPI Section Ch, Week 9220, Derwent Publications Ltd., London, GB; Class E16, AN 1992-162202 & JP-A-04 096 989 (SANYO ELECTRIC CO) 30. März 1992 *
Derwent Abstract of JP 04/096,989, Mar. 1992.
Pannock et al, "Performance of Chlorine-free Binary Zeotropic Refrigerant Mixtures", Chem. Abs. 119((22):228807e, Dec. 1991.
Pannock et al, Performance of Chlorine free Binary Zeotropic Refrigerant Mixtures , Chem. Abs. 119((22):228807e, Dec. 1991. *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5705086A (en) * 1996-04-16 1998-01-06 Mobil Oil Corporation Refrigeration oils comprising esters of hindered alcohols
US6176102B1 (en) * 1998-12-30 2001-01-23 Praxair Technology, Inc. Method for providing refrigeration
US6327866B1 (en) 1998-12-30 2001-12-11 Praxair Technology, Inc. Food freezing method using a multicomponent refrigerant
WO2003027206A2 (en) * 2001-09-25 2003-04-03 American Standard International Inc. Replacement refrigerant for r410a
WO2003027206A3 (en) * 2001-09-25 2004-03-04 American Standard Int Inc Replacement refrigerant for r410a
US20040061091A1 (en) * 2002-10-01 2004-04-01 Tieken James B. Refrigerant blend

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AR247910A1 (en) 1995-04-28
FI933155A (en) 1994-01-12
CA2100316A1 (en) 1994-01-12
LV10787A (en) 1995-08-20
HU9301945D0 (en) 1993-09-28
HUT67329A (en) 1995-03-28
AU663783B2 (en) 1995-10-19
TW290585B (en) 1996-11-11
EP0579072B1 (en) 1996-01-24
TR26928A (en) 1994-08-24
LV10787B (en) 1996-06-20
JO1752B1 (en) 1993-10-30
BR9302818A (en) 1994-02-16
AU4012293A (en) 1994-01-13
ES2082559T3 (en) 1996-03-16
LTIP773A (en) 1994-07-15
MX9304121A (en) 1994-03-31
KR940002338A (en) 1994-02-17
PL299632A1 (en) 1994-02-21
MY109007A (en) 1996-11-30
JPH06166868A (en) 1994-06-14
FI933155A0 (en) 1993-07-09
ATE133444T1 (en) 1996-02-15
SK56393A3 (en) 1994-05-11
DE4222855A1 (en) 1994-01-13
LT3082B (en) 1994-11-25
EP0579072A1 (en) 1994-01-19
CZ102293A3 (en) 1994-02-16
SI9300371A (en) 1994-03-31
DE59301495D1 (en) 1996-03-07
CN1081460A (en) 1994-02-02
IL105948A0 (en) 1993-10-20
IL105948A (en) 1996-06-18

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